Method of retarding fouling of a substrate surface

ABSTRACT

A method of retarding the fouling of a substrate surface and resulting deposits thereon, where the said fouling and deposits are formed by contacting the substrate surface in the presence of water and carbon dioxide with at least one of the amine compounds consisting of amine compounds having primary amino groups, secondary amino groups and primary and secondary amino groups, the method being characterized by treating the said surface and any resulting deposits thereon with at least one organic acid selected from aliphatic dicarboxylic acids having from two to 10 carbon atoms, tricarboxylic acids having six to 10 carbon atoms, alkanoic acids having from four to eight carbon atoms, unsaturated organic acids having three to eight carbon atoms and phenol. The method has particular utility in treating mold surfaces used for preparing polyurethane articles.

United States Patent Watters Feb. 8, 1972 [54] METHOD OF RETARDING FOULING OF A SUBSTRATE SURFACE [72] Inventor: Larry 11. Watters, Akron, Ohio [73] Assignee: The Goodyear Tire & Rubber Company [22] Filed: Aug. 1, 1969 [21] Appl. No.: 846,919

Related [1.8. Application Data [63] Continuation-in-part of Ser. No. 673,964, Oct. 9, 1967, Pat. No. 3,475,217, and a continuation-in-part of 827,885, May 26, 1969.

[52] US. Cl ..134/42, 134/3, 134/28, 264/39 [51] Int. Cl. ..B08b 3/00, C23g 1/02 [58] FieldofSearch ..l34/3,28,41,42;260/540, 260/541, 542, 711; 264/39, 130; 252/142, 193

[56] References Cited UNITED STATES PATENTS 1,952,417 3/1934 Chandler ..134/3 2,417,468 3/1947 Canzianietal. ..l34/28 Pollard et a1 ..264/39 Booth et a] ..l34/28 X Primary Examiner-Morris O. Wolk Assistant Examiner-Joseph T. Zatarga Att0mey-F. W. Brunner and Henry C. Young, Jr.

[57] ABSTRACT A method of retarding the fouling of a substrate surface and resulting deposits thereon, where the said fouling and deposits are formed by contacting the substrate surface in the presence of water and carbon dioxide with at least one of the amine compounds consisting of amine compounds having primary amino groups, secondary amino groups and primary and 13 Claims, No Drawings METHOD OF RETARDING FOULING OF A SUBSTRATE SURFACE This application is a continuation-in-part of Ser. No. 673,964, filed Oct. 9, 1967 now US. Pat. No. 3,475,2 l 7 dated Oct. 28, 1969, and 827,885, filed May 26, 1969.

This invention relates to a method of retarding the modification or fouling of a substrate, particularly where the modification or fouling of the substrate is caused by its exposure to compounds containing primary and secondary amino groups.

Various materials can be molded on substrates to form molded articles. However, it is known that various materials when molded on a substrate can modify the surface of the substrate to inhibit the ability of the surface to release the molded articles. For example, it was observed that when polyurethane reaction mixtures prepared from reactive hydrogen-containing polymeric materials, organic polyisocyanates, and polyamine compounds are cast on a substrate, the surface of the substrate can become modified so that the ability of the substrate or mold surface to release the molded article is inhibited and also the surface definition of the mold is reduced. (The term surface definition" used in this specification refers to the distinctness and sharpness of an outline of a surface.) Thus, in a molding operation as successive molded articles are formed from the same mold, the mold surface is progressively modified and subsequent successive molded articles are more difficult to release from the mold surface, and the mold surface imparts progressively inferior decorative definitions to the surface of the resulting molded articlesv As the mold surface becomes progressively modified, eventually a molded article becomes sufficiently adhered to the mold surface that it cannot be removed from the mold without destroying a portion of the mold or molded article.

I have now discovered that such substrate surfaces have been modified when the substrate surface was exposed in the presence of water and carbon dioxide to compounds referred to in this specification as substituted methyl amine compounds where the said substituted methyl amine compounds are characterized by the test which comprises forming one liter of a solution containing from about 10 to about parts by weight of the substituted methyl amine compound per lOO parts by weight of methyl ethyl ketone, aging the solution for 8 hours at C., warming the solution to C. and passing gaseous carbon dioxide at about 25 C. through the solution at a rate of about one gaseous liter per minute to form a turbidity in the solution within 60 minutes. I

Representative substituted methyl amine compounds have the structure of the formula l where R R and R are individually selected from the group consisting of (a) hydrogen radicals, alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals. Representative of such radicals are alkyl radicals having from one to forty carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl, heptyl, octyl, duodecyl and tetracontyl radicals; cycloalkyl radicals such as cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane; aryl radicals such as phenyl and naphthyl radicals; alkaryl radicals such as tolyl and xylyl radicals, and aralkyl radicals such as benzyl radicals; and (b) substituted alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals where the substituents are selected from at least one of the group consisting of hydrogen, carbon, oxygen, sulfur, fluorine, chlorine, bromine, iodine, and phosphorous. Representative examples of such substituted radicals are amino radicals, imino radicals, and radicals containing amino groups, imino groups, halo groups, ether groups, and thioether groups.

The preferred substituted methyl amines are all primary diamines having their amino groups attached to nonbenzenoid carbon atoms which produce turbidity in the hereinbefore described test.

Further representative examples of the said substituted methyl amine compounds are compounds prepared by the method which comprises reacting the substituted methyl amine compound of Formula l with an aldehyde or ketone. Various aldehydes can be used, representative of which are formaldehyde, acetaldehyde, propionaldehyde and benzaldehyde. Various ketones can be used representative of which are acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl n-amyl ketone, methyl-i-amyl ketone and acetophenone. These compounds are generally called aldimines and ketimines.

Representative examples of the various substituted methylamine compounds are ethylene diamine, hexamethylene diamine and dimethyl hexamethylene diamine; isophorone diamine, 1,4-cyclohexane bis methylamine, 4,4- diamino-dicyclohexyl methane, meta xylene diamine, paraxylene diamine, tetrachloroparaxylene diamine, cyclobutane- 1,2 bis methylamine, menthane diamine, imino bis propylamine, bis(amino propyl) piperazine, diethylene triamine, triethylene tetramine and tetraethylene pentamine.

Because the substrate surface, when it isso modified, can have a substantially reduced ability to release molded articles, it is therefore an object of this invention to provide a method of rejuvenating such a modified substrate surface where the said substrate surface has been modified by contacting the substrate in the presence of carbon dioxide and water with the substituted methyl amine compounds. It is another object of this invention to provide a method rejuvenating such a modified substrate surface without appreciably degrading the substrate surface where the substrate surface is a polymeric material.

Although the theory of the substrate surface modification is not thoroughly understood, my discovery discloses the modification to be in the nature of a deposit adhered to the surface of a substrate. The deposit, for example, can be adhered to the surface of an impermeable substrate surface and the deposit can be adhered to the surface and within the pores ofa surface of a permeable substrate surface. The so-called deposit appears to become physically bonded to the substrate. The problem of the substrate surface modification is particularly evident when pores of a mold surface become so modified. Where such a mold surface is a flexiblepolymeric material, the deposits can continue to form and build up in its pores and cause the surface of the mold to deform, thereby producing an inferior decorative surface definition to the molded article.

In accordance with this invention, it has been found that a method of retarding the fouling of a substrate surface and rejuvenating the said surface when having resulting deposits thereon, where the said fouling and deposits are formed by contacting the substrate surface in the presence of water and carbon dioxide with at least one of the amino compounds consisting of amino compounds having primary amino groups, secondary amino groups and primary and secondary amino groups comprises treating the said surface and any resulting deposits thereon with at least one organic acid selected from aliphatic dicarboxylic acids having from two to 10 carbon atoms, tricarboxylic acids having six to 10 carbon atoms, alkanoic acids having from one to 8 carbon atoms, unsaturated organic acids having three to 8 carbon atoms and phenol. The said fouling is particularly retarded where the substrate surface is contacted with a mixture of at least one of the said amine compounds and a liquid chlorosubstituted olefin, and then subsequently treating the substrate surface with at least one of the said organic acids.

Representative of various organic acids for treating the surface are aliphatic dicarboxylic acids such as oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, and sebacic; tricarboxylic acids such as citric; unsaturated organic acids such as acrylic, crotonic, maleic and fumaric; alkanoic acids such as formic, acetic, propionic, butanoic, pentanoic, hexanoic, heptanoic and octanoic; and halo-substituted alkanoic acids such as chloroacetic, dichloroacetic, trichloroacetic, fluoroacetic, difluoroacetic, trifluoroacetic, a fiuoropropionic, a chloro propionic, a bromo propionic, a iodo propionic, a iodo propionic, a-beta dichloro propionic, a-beta dichloro propionic, a-beta dibromo propionic, a chloro butyric, a fluoro butyric, a-beta dichlorobutyric and 04- beta dibromobutyric.

The lower saturated alkanoic acids, formic, acetic and propionic, are differentiated as a separate class from the other acids by their properties, particularly since their melting point is less than 20 C., their molecular weight is less than 75, and they are classified as infinitely soluble in water and ethanol at 20 C. Even the higher saturated alkanoic acids having four to eight carbon atoms are differentiated from the lower alkanoic acids because of their increased molecular weight and substantially reduced solubility as evidenced by their very limited solubility in water at 20 C.

Treatment is typically effected with a mixture of the acid and solvent, particularly where the acid melts above about 20 C. Suitable organic solvents are preferably substantially inert solvents which will penetrate the harmful deposits, in which the acid is soluble to at least percent by weight of the acid at 25 C. and do not detrimentally chemically react with or excessively dissolve the substrate. Representative examples are liquid saturated and unsaturated aliphatic hydrocarbons, liquid cycloaliphatic hydrocarbons, liquid halo-substituted saturated and unsaturated aliphatic hydrocarbons, liquid aromatic hydrocarbons, liquid halo-substituted aromatic hydrocarbons, liquid ketones, carbon disulfide and their mix tures.

The various liquid halo-substituted hydrocarbon solvents, particularly the chlorosubstituted olefins, are also useful in the practice of this invention for mixing with the said amine compounds, exemplary of which are dichloroethylene trichloroethylene l,l,2,2-tetrachloro methylene, chloroform, methyl chloroform, dichloro methane, 1,2-dichloro ethane, trichloro ethane and 1,1,2,2-tetrachloroethane. Chloroform is particularly useful when used with trichloroacetic acid at concentrations of from about 2 to about 50 weight percent of the acid.

Representative of saturated aliphatic hydrocarbon solvents are liquid hydrocarbons containing from four to eight carbon atoms such as pentane, hexane, heptane, and octane; representative of unsaturated aliphatic hydrocarbons are those containing from five to eight carbon atoms such as pentene, hexene, heptene and octene; representative of cycloaliphatic solvents is cyclohexane; representative of aromatic hydrocarbons are benzene, toluene and xylene; representative of liquid ketones are acetone, methyl ethyl ketone, methyl isoamyl ketone, methyl isobutyl ketone and diisobutyl ketone; representative of liquid alcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol.

When the organic acids are used in the absence of solvents or used as a mixture with solvents, it is preferred that the organic acids and the mixtures of organic acids and solvents contain less than about 50 percent by weight of water based on the acid and more preferably that they are essentially waterfree although traces of water can be present such as up to about 10 percent by weight of water based on the acid.

A mixture of organic acid and solvent can be used to treat the substrate or modified substrate at various temperatures, such as 0 C. to 100 C., although it is usually more desirable to effect the treatment at a temperature of from about C. to 80 C. Various pressures can be used, such as atmospheric or above or below atmospheric. Usually the autogeneous pressure developed by the system is satisfactory.

Various substrate surfaces having the deposits formed therein can be treated by the method of this invention. The invention has particular utility where the substrate surface is a polymeric material. It is preferred that the substrate surface is suitable for molding articles and therefore not chemically reactive with the compounds used to prepare the molded articles. It is also preferred that the substrate surface will not tightly adhere to the molded articles. For example, if the molded articles are to be of an epoxy compound or of polyurethane, it is usually desired that the substrate will not tightly adhere to an epoxy compound or to a polyurethane when cured. Substrates for this purpose can have surfaces of materials known to those skilled in the art which do not tightly adhere to molded epoxy compounds and polyurethanes such as polyethylene, polypropylene and silicone rubber or the substrates can be made of these materials or other materials which have a surface coated with various suitable release agents and parting films also known to those skilled in the art.

A wide range of other substrate surfaces can be used which are preferably coated with the release agents and used to mold articles. Such substrate surfaces are known to those skilled in the art. Representative examples of such various substrate surfaces include the various solid metals and their alloys, cured millable gum silicone rubbers, cured natural rubber and rubberlike polymers, thermoplastic polymeric materials and thermoset plastic materials.

Most, if not all, of the substrate materials have pores in their surfaces and therefore are permeable to some degree. Representative examples of some of the various metals are aluminum, iron and their alloys. Representative ofrthe various rubberlike polymers are rubbery polyurethanes and rubbery cured polymers and copolymers such as rubbery polymers of conjugated dienes including polybutadiene, polyisoprene, chloroprene, copolymers of butadiene and isoprene which contain a major portion of butadiene, particularly copolymers of butadiene and styrene of the hot and cold SBR type which contain from about 60 to about percent byweight of butadiene, copolymers of butadiene and acrylonitrile, butyl rubber, which is a polymerization product of a major portion of a monoolefin such as isobutylene and a minor portion of a diolefin such as butadiene or isoprene copolymers of ethylene and propylene, and terpolymers of ethylene, propylene and a diene. Representative of the various thermoplastic and thermoset polymers are the polyurethanes, the various epoxide resins and epoxide varnishes, polymeric polyesters and polymers formed by the open ring polymerization of unsaturated alicyclic compounds having from one through three carbon-to-carbon double bonds in the alicyclic ring such as polyoctenamers and polydodecenamers.

Representative of the various release agents for the substrate surfaces are those that do not adhere to the epoxy compounds and polyurethanes and which do not react with polyu rethane reactants and epoxy compounds to reduce the flexibility, tear, tensile strength and cold temperature properties of cured polyurethane compositions and epoxy compounds. Any of the many releasing agents or parting agents known to those skilled in the art to be useful in preparing epoxy and polyurethane castings may be used in this invention provided they meet the above requirements.

Some of the many suitable release agents include the polyethylene and polypropylene waxes and emulsions, natural waxes, synthetic waxes, dimethyl silicone fluids, greases and higher polymers, soya bean fatty acid types or vegetable cephalin and lecithin, soaps, fluorocarbons, polyvinyl alcohol and fluorosilicones.

In the practice of this invention, it has been found that even if a substrate is coated with a release agent, when the release agent coating is contacted in the presence of water and carbon dioxide with the substituted methyl amine compounds, the release agent coating can apparently be penetrated and the surface of the substrate can still become modified by the formation of the deposits on the surface and within the pores of the substrate. When the surface of a substrate becomes modified with deposits in this manner the surface definition of the substrate is reduced and molded articles are more difficult to release from the substrate. Such a modified substrate surface can be treated by the method of this invention to substantially remove the so-called deposits when formed on the substrate surface or within its pores, following which a release agent coating can be reapplied to the substrate surface.

As hereinbefore described. the deposits formed on and within substrate surfaces prepared from silicone rubbers can be treated by the method of this invention. Silicone rubbers are a class of materials well known to those skilled in the art as rubbery cured poly(organosiloxanes). The silicone rubbers are particularly suitable substrates for molding epoxy and polyurethane articles because they can form flexible substrates which do not tightly adhere to such articles after the articles are molded. Such substrates may be produced by curing room temperature vulcanizing liquid silicone rubbers or millable gum silicone rubbers well known to those skilled in the art.

Representative of the room temperature vulcanizing liquid silicone rubbers are those described as organopolysiloxane compositions containing silicon-bonded hydroxyl groups which can be cured by metal salts of organic carboxylic acids, by quarternary ammonium compounds or by epoxide containing compounds in the presence of primary, secondary or tertiary amines.

In general, these silanol-containing organopolysiloxanes contain an average of from about 1.0 to 198 organic groups attached to silicon through silicon-carbon linkages, and contain an average of from 0.01 to l silicon-bonded hydroxyl groups per silicon atom. Alternatively, some of the siliconbonded hydroxyl groups can be replaced with alkoxy groups or with pendant hydrogen atoms.

These compositions can be described as having the average formula where R is a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical, R is an alkyl radical containing from one to eight carbon atoms, a has a value of from 1.0 to 1.98, b have a value from 0.01 to l, c has a value offrom to 0.99, the sum of b-l-c is from 0.01 to l, and the sum of a+b+c is from 1.01 to 2.1. Included among the radicals represented by R are, for example, alkyl radicals, e.g., methyl, ethyl, propyl, butyl, octyl, decyl, etc., radicals; aryl radicals, e.g., phenyl naphthyl, xylyl, tolyl, etc., radicals; aralkyl radicals, e.g., benzyl, phenyl-ethyl, styryl, etc., radicals; alkenyl radicals, e.g., vinyl, allyl, etc., radicals; cycloaliphatic hydrocarbon radicals, e.g., cyclohexyl, cycloheptyl, cyclohexenyl, etc., radicals; cyanoalkyl radicals, e.g., cyanoethyl, cyanomethyl, cyanopropyl, etc., radicals; halogenated monovalent hydrocarbon radicals, e.g., chloromethyl, bromomethyl, chloroethyl, chlorophenyl, tetrachlorophenyl and dibromophenyl radicals.

Representative of the millable silicone rubber gums are those described as: organo-substituted polysiloxanes, commonly called dialkyl or alkyl-aryl polysiloxane gums. The substituted groups are usually at least 50 percent in number methyl groups. The remainder of the groups are usually methyl or methyl with to percent phenyl or methyl with phenyl and vinyl, or methyl, vinyl or cyanopropyl groups, methyl vinyl and ethyl groups, or methyl and trifluoropropyl groups. The millable silicone rubber gums can be shown by the empirical formula /SiO R n where R and R are selected from the class consisting of the methyl and ethyl groups, the halogen and nitrile substituted alkyl groups containing from one to four carbon atoms, phenyl, halogenated phenyl, vinyl and cyclohexenyl groups and n is a large number. R and R may, if desired, be predominately or entirely methyl groups.

The millable gum silicone rubbers are generally cured by reacting the poly(organosiloxane) with a peroxide such as 2,4- dichlorobenzoyl peroxide, di-(tertiarybutyl)perbenzoate, tertiarybutyl perbenzoate, benzoyl peroxide or dicumyl peroxide.

Usually about from 0.5 to 15 and preferably 1.0 to 3.0 parts of curing agent per parts by weight of silicone rubber are used, depending on the percentage of unsaturated substitution present.

Various fillers can be added to the silicone rubber before curing, typical of which are, for example, fume silicas, silica aerojels, organo-silane modified silicas, barium and cadmium titanates, zirconates and stannates; diatomaceous earth, clays, calcium carbonate, finely ground quarts, barites, iron oxide, zinc oxide, titanium dioxide and mixtures thereof.

The cured silicone rubbers have various physical properties. For example, they may have tensile strengths from about 100 to about 1,000 pounds per square inch, elongations of from about 100 to 600 percent and a Durometer hardness, Shore A scale offrom about 20 to about 60.

It has been found that if the substrate surface having the deposit thereon is a silicone rubber, it is preferred that the organic acids are concentrated so that they will wet and penetrate the silicone rubber surface. Preferably they contain less than about 5 weight percent of water based on the acid.

When molded polyurethane articles are prepared by applying a polyurethane reaction mixture containing at least one of the substituted methyl amine compounds to a substrate mold surface in the presence of atmospheric water and carbon dioxide, curing the reaction mixture and removing the molded polyurethane article from the mold, the harmful deposits can progressively form and build up on the substrate surface and adhere to successive molded articles. Diamines having amine groups attached to nonbenzenoid carbon atoms are used as curatives or chain extenders for polyurethanes and therefore are used to form polyurethane reaction mixtures.

Thus, in the practice of this invention, a method of removing deposits from substrate mold surfaces, where the said deposits are formed by contacting the substrate surface in the presence of water and carbon dioxide with the polyurethane reaction mixture, curing the reaction mixture, and removing the resulting cured polyurethane article from the substrate surface, comprises treating the said deposits with the acids used in this invention and drying the substrate surface. If the deposits are formed on a permeable mold substrate surface such as a silicone rubber by the molding of a polyurethane containing the substituted methyl amine, the said deposits can be substantially removed from its pores.

The polyurethane reaction mixtures which can be used in the practice of this invention to prepare mold substrate surfaces and which can be used to prepare molded articles on substrate surfaces are prepared from a reactive hydrogen-containing polymeric material, an organic polyisocyanate and at least one of the substituted methyl amines which are diamines having amino groups attached to nonbenzenoid carbon atoms. It is to be understood that the polyurethanes referred to in this specification may also contain polyurea linkages.

In accordance with this invention, a nonreactive solvent, particularly a liquid chloro-substituted olefin is added to the reaction mixture so that it will be fluid. The preferred chl0rosubstituted olefins have been hereinbefore described as those desired for mixing with the said amine compounds.

Generally, sufficient solvent is added to form a solution containing from about 35 to about 65 percent solids. However, a higher or lower concentration of solids can be used, depending upon the reactants used and upon the intended use of the solution.

The reactive hydrogen-containing polymeric material used comprises at least one member selected from the group consisting of polyester polyols, polyesteramides, polyether polyols, dihydroxy terminated polymers of conjugated diene hydrocarbons, and castor oil. The reactive hydrogen-containing material generally used has a molecular weight between about 700 and about 5,000 and, usually, between about 1,000 and about 3,000. Generally the polyester polyols are the preferred active hydrogen-containing material where high strength and solvent resistance are desired.

Representative examples of polyester polyols are the condensation products of low molecular weight polyols with an organic polycarboxylic acid or anhydride. Representative low molecular weight polyols are glycols such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, decamethylene glycol, etc. Representative examples of the organic dicarboxylic .acids that can be used are succinic acid, glutaric acid, adipic acid, phthalic acid, terephthalic acid, isophthalic acid, suberic acid, sebacic acid, pimelic acid, and azelaic acid. The anhydrides of such acids can be used in place of the acid. lf desired, from about one to percent by weight of a triol or higher polyfunctional polyol or polyfunctional acid can be present to produce branching in thepolyurethane polymer.

Polyether polyols useful in preparing the polyurethanes used in this invention can be prepared by polymerizing or copolymerizing alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxides, by polymerizing or copolymerizing the low-molecular weight glycols, or by the reaction of one or more such alkylene oxides with the glycols or with triol, or with a polycarboxylic acid such as phthalic acid.'The polyether polyols include polyalkylene-aryl ether glycols or triols, polytetramethylene ether glycols, polyalkylene ether-thioether glycols or triols, and alkyd resins. Generally, the polytetramethylene ether glycols are the preferred polyether glycols.

Representative examples of dihydroxy-terminated polymers of conjugated diene hydrocarbons are dihydroxy-terminated polymers of isoprene and butadiene and their copolymers with minor amounts of vinyl compounds such as styrene and acrylonitrile.

Polyesteramides may be prepared by reacting a diamine, a glycol, and a dicarboxylic acid under conditions which will remove the water of condensation. Representative glycols and dicarboxylic acids useful in preparing polyesteramides are those useful in preparing polyesters, examples of which have already been shown. Various diamines may be used in forming the polyesteramides, representative of which are ethylene diamine, hexamethylene diamine, decamethylene diamine, cyclohexyl diamine, phenylene diamine, methylene dianiline, toluidine diamine, dichlorobenzidine, and methylene-bischloroaniline.

The organic polyisocyanates used to prepare the polyurethanes include various organic diisocyanates and mixtures thereof. Generally the organic diisocyanates are preferred. The organic polyisocyanates can be aromatic, aliphatic, or cycloaliphatic or combinations of these types.

Representative examples of such polyisocyanates include the toluene diisocyanates, m-phenylene diisocyanate, 4- chlorol ,3-phenylene diisocyanate, 4,4'-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10- decamethylene diisocyanate, l,4-cyclohexylene diisocyanate, 4,4-methylene bis (cyclohexylisocyanate) and 1,5-

tetrahydronaphthalene diisocyanate, and mixtures of such diisocyanates. For the purpose of the present invention, the toluene-diisocyanates, diphenylmethane-4,4'-diisocyanate and 3,3'-dimethyl-4,4-bisphenylene diisocyanate, are generally preferred although the diisocyanate having isocyanato groups connected to nonbenzenoid carbon atoms are preferred where color retention is important.

The polyurethane polymers are usually prepared by forming a liquid polyurethane reaction mixture by reacting a reactive hydrogen-containing polymeric material with a polyisocyanate to form an isocyanate terminated polyurethane which is then mixed with the diamine. The reaction mixture is then cured to form the polyurethane polymer. The isocyanate terminated polyurethanes can be prepared by reacting the reactive hydrogen-containing polymeric material with the organic polyisocyanate in proportions such that the ratio of isocyanate groups to the reactive hydrogen-containing groups of the reactive hydrogen-containing polymeric material is from about l.l/l to about 12/1 and preferably about 1.2/1 to about 2.5/1. These materials are generally reacted at temperatures from about 20 C. to about C. The reactive hydrogens of the reactive hydrogen-containing polymeric material are supplied by hydroxyl groups and amino groups.

Other methods known to those skilled in the art of preparing polyurethanes with or without solvents being present may also be used.

Any of the nonreactive solvents normally used in making paints which are suitable for spraying are useful as diluents for the isocyanate-terminated polyurethanes of this invention. Representative examples of these are benzene, toluene, the paraffinic naphthas, the naphthenic naphthas, the aromatic naphthas, ethyl formate, propyl formate, butyl formate, amyl formate, ethyl acetate, propyl acetate, methyl acetate, butyl acetate, amyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isoamyl ketone, cellosolve acetate, dioxane, lower nitraparaffins, etc. Mixtures of solvents may be used to obtain satisfactory spreading properties and evaporation rates. particularly when the polyurethane is to be used as a spray composition and applied to a suitable surface.

The isocyanate-terminated polyurethane, sometimes called a prepolymer, is usually dissolved or dispersed in the solvent to form a solution or dispersion which is then reacted with the diamine to form a cured polyurethane. The diamine is usually added to the isocyanate-terminated polyurethane in a ratio of from about 0.5/1 to about 1.5/l and, preferably, about 0.8/1 to about l.O/l amine groups of the diamine for each isocyanate group in excess of the reactive hydrogen groups of the reactive hydrogen-containing polymeric material.

The following illustrative examples are set forth to further exemplify the objects and advantages of the invention. The parts and percentages are by weight unless otherwise indicated.

EXAMPLES l-Xll Liquid polyurethane reaction mixtures were prepared by a prepolymer method with various diamines having amino groups attached to nonbenzenoid carbon atoms, cast onto various substrate surfaces in the presence of atmospheric water and carbon dioxide, cured to form solid polyurethanes, and the solid polyurethanes were released from the substrates. For the purpose of this disclosure these polyurethane castings are referred to as Examples I through Xll and are shown in Table l. The substrates used in these examples are those which normally do not tightly adhere to the cured polyurethane. For Examples l through X a silicone rubber substrate was used, in Example Xl a natural rubber substrate was used, and in Example Xll a cured polyurethane substrate was used. In both of Examples XI and Xll, a soya bean fatty acid release agent was coated over the substrate surface.

ln Example l, 14 successive polyurethane articles, hereinafter also referred to as parts, were molded on the silicone rubber substrate surface. The polyurethane articles were molded on the substrate at a rate of about 10 molded articles per day by applying a liquid polyurethane reaction mixture to the substrate surface and curing the reaction mixture for about 30 minutes at 60 C. At the end of each day the mold substrate was allowed to rest for about l2 hours. At the end of the third day 29 molded articles had been prepared. Each of the molded polyurethane-articles had a successively reduced gloss progressively ranging from a gloss of 3 gloss units for the first molded article to a gloss of about 0.5 gloss units for the 29th molded article. The gloss was determined with a 60 glossmeter according to ASTM Method D523-66T. The sil icone rubber moldsurface during the successive molding operations became progressively harder and assumed a white discoloration. The molded polyurethane articles became progressively more difficult to release from the silicone rubber substrate. Under microscopic examination after the 29th molded article, the silicone rubber surface was observed to be distorted, swelled, and cracked and to be impregnated with a white crystalline deposit.

The 30th polyurethane molded article was prepared on the substrate the following day. The 30th cured polyurethane article adhered to the substrate with sufficient tenacity to tear the silicone rubber mold substrate upon its removal.

Compound Parts by Weight l,4-Butane diol adipate having a molecu lar weight of about 2,000 and an hydroxyl number ofabout 56 l,4-Butane diol adipate having a molecu lar In mp g IX the Silicone rubber Substrate was weight of about L000 and an hydroxyl number ofabuut H2 27 washed with various or anic acids and or anic acid-solvent '-Di y h xylmezh n i ocyan te 21.5

g g mixtures after about each l5th polyurethane molded article or f' l V 50 part was prepared on its surface by the method of Example I. 31:53 my polymer used as As shown in Table l, the silicone rubber substrate maintained 1 0 its good release properties but the gloss of the molded polyu- I I rethane articles decreased from a gloss of 3 gloss units to a The 'dlcyclohelfyl methane dllsocyanate was heated to gloss ofo gloss unim about 90 (I. and mixed with the l,4 butane diol adipate In Example X after about each pans, the mold was polymers whlch had also been preheated to about 90 C. and washed with a mixture of glacial acetic acid and chloroform. 15 allowed to react for about 50 mmutes at about 1500 The After about each 75 parts, the mold surface was first washed m'xture was degfissed for about 45 mnlules at a reduced with the glacial acetic acid mixture followed by washing the of abolft 28 i of mercury- Thls prepolymer was mold with formic acid AS shown in Table I after 600 parts, then dissolved in the dichloromethane to Which the small the silicone rubber substrate showed excellent release properzffiounzoilacquer h ,been added' ties as to its ability to release the polyurethane molded articles e ore ldpphcauon F mold Substrate the polyu and the molded polyurethane articles had a gloss of 2.5 gloss {l g g f 'g i about 17 parts ofa units compared to a gloss of 3.0 units for the original casting We so u Ion w consiste o from the silicone rubber substrate.

For Examples XI and Xll the substrates were washed with a 7 by mixture of 50 percent by weight glacial acetic acid in acetone I I after about each 40 parts. The mold release agent was applied to the substrate surface before each polyurethane article was molded on the silicone rubber substrate. v The flexible silicone rubber molds used for Examples l to X The natural rubber substrate used Example XI was were prepared by casting a liquid room temperature vulcaniz- Prepared from the followmg? ing silicone rubber over the surface of a shaped leather grained substrate. The silicone rubber was cured at about 25 cmlmund by Weigh C. for 8 hours and was easily removed from the leather grained substrate to form a flexible, self-releasing silicone Nuwml Wigwam Potassium eate 2.0 rubber mold having an inner surface, the said inner surface 10% mm hydroxidg 05 being a negative reproduction of the leather grained surface of sum" containing curing agent 2.0 the said substrate. The molds of silicone rubber were then x 1.0 further postcured for about 3 days at about 250 C. and for 8 EM] hours at about C. The inner surface of the silicone rubber 40 molds had a gloss of 30 gloss units. The liquid room tempera- The cured polyurethane substrate used in Example Xll was ture curing silicone rubber used to prepare the flexible molds prepared from a prepolymer of a polybutadiene polyol and was prepared by mixing components A and B of RTV 588, 4,4'-methyl-bis-(cyclohexylisocyanate), a 2-ethyl-l,3-hexane (obtained from The Dow Corning Com a i edi tel diol curative, and dibutyl tin dilaurate asacatalyst.

TABLE 1 Freg uencly; .Afbility tobrelease 0 was a ter num er of Examples Mold substrate Diamine Acid wash parts molded parts I Silicone rubber None 1/15 Adhesion/30 parts.

1 Glacial acet 1c acid 1/15 Excellent/500 parts.

Glacial acetic plus 0 1/15 D0.

97% formic". 1/15 Excellent/100 parts. 97% propionic 1/15 Do. I pa xylene dtamine Glacial acetic plus 0 1/15 Excellent/600 parts. 4,4 -diam1no dtcyclohexyl methane. 0 1/15 Excellent/100 parts. Mentliane diamme ..do 1/15 Do. Diamine A-100*. "do 1/15 Excellent/80 parts. X do Meta-para xylene dlamme Glaclal acetic plus CHCI; (60%) and 1/75 Excellent/600 parts.

97% formic acid. XI Natural rubber latex .do Glacial acetic and acetone 1/40 Excellent/300 parts. XII Polyurethane .do do 1/40 Do.

A long chain fatty acid dlamine obtained from General Mills, Inc.

EXAMPLES Xlll-XXX To illustrate deposit formation by various substituted methyl amines in the presence of water and carbon dioxide in Examples Xlll to XXX small l inch by l inchsquares of silicone rubber were prepared by casting and curing a liquid room temperature vulcanizing silicone rubber prepared according to the method used in Examples 1 to Xll.

For Example Xll], a liquid polyurethane reaction mixture was prepared, cast and cured on the surface of a silicone rubber square. The polyurethane reaction mixture was cured at about 25 C. for about 12 hours. The layer of cured polyurethane did not tightly adhere to the surface of the silicone rubber square and was easily released and removed from the said silicone rubber surface.

For Examples XIV to XXX, the silicone rubber squares were immersed in solutions of various compounds having amino groups attached to nonbenzenoid carbon atoms for about 96 hours at about 30 C. The squares were then dried at about 25 C. for about 48 hours in the atmosphere which contained atmospheric water and carbon dioxide.

When the silicone rubber squares were dry, the appearance of their surfaces was noted in Table 2 and according to the method of Example I, a liquid polyurethane reaction mixture was prepared. cast and cured on their surfaces according to the method of Example I. In all of the Examples XIV to XXX the cured polyurethanes released from the silicone rubber with greater difficulty than from the silicone rubber which had not been treated with the compounds having amino groups. In all of the Examples XIV to XXX the treated silicone rubber squares showed visual evidence ofa deposit formation.

The silicone rubber squares of Examples XIV to XXX were then washed with a solution of 50 weight percent glacial acetic acid and 50 weight percent chloroform and dried.

After the acetic acid wash the liquid polyurethane reaction mixture was cast and cured on the surface of the silicone rubber squares according to the method of Example Xlll. In all of the Examples XIV to XXX, the cured polyurethane layer easily released from the silicone rubber squares.

TABLE 2 Appearance after Treatment with piperazine Exam le Amine Compound Amine Compound Xl\ l.4-cyclohexane his White. crusty,

mcthylamine migratory stain XV 4.4 diamino dicyclo- White, crusty,

hexyl methane migratory stain XVI Menthane diamine Pink. crust, white penetrating stain XVII Triethylene tetramine White penetrating stain XVIII Diethylene triamine White penetrating stain XIX Tctraethylene pentamine White penetrating stain XX Trimethylhexamethylene White penetrating diamine stain XXI Isophorone diamine White penetrating stain XXII Diamine A-IOO White penetrating stain XXIII Ethylene diamine White penetrating stain XXIV Cyclobutane-l .Z-his- White penetrating methylamine stain XXV Meta xylene diamine White penetrating stain XXVI Para xylene diamine White penetrating stain XXVII Meta-para xylene White penetrating diamine stain XXVIII I Tetrachloro paraxylenc White penetrating diamine stain XXIX lmino-his propylamine White penetrating stain XXX Bis (amino propyl) White penetrating stain EXAMPLES XXX XXXIX Squares of silicone rubber were prepared according to the method of Example XIII and immersed in a solution of metaparaxylene diamine at about 30 C. for about 96 hours. The squares were then dried at about 25 C. for about 48 hours in the presence of atmospheric water and carbon dioxide.

When the silicone rubber squares were dry, their surfaces were dull and had a white crusty appearance. When a polyurethane reaction mixture was cast and cured on the surface of one of the silicone rubber squares according to the method of Example XIII the resulting cured polyurethane released from the silicone rubber with difficulty.

The modified silicone rubber squares were washed with various organic acids as shown in Table 3, and dried after the acid wash. A polyurethane reaction mixture was cast and cured on the surfaces of the silicone rubber squares according to the method of Example Xlll. In all of the Examples XXXI to XXXIX, the cured polyurethane easily released from the silicone rubber squares.

In Examples XXXVII, XXXVIII, and XXXIX, the modified silicone rubber squares had been successively washed with successively lower acids. In these examples not only were the release properties of thesilicone rubber squares rejuvenated but their original gloss was substantially restored or substantially improved. Except for Example XXXIV where the dilute acid wash did not rejuvenate the silicone rubber surface, in Examples XXXI to XXXVI the release property of the silicone rubber squares was rejuvenated but their surfaces remained dull.

Silicone rubber substrate surfaces were prepared according to the general method of Examples I-XXXIX. The prepared silicone rubber surfaces were then purposely contacted with meta para xylene diamine in the presence of water and carbon dioxide for 16 hours at about 25 C. in order to cause a substantial stain to appear on the surface of the silicone rubber, thereby fouling the surface with such a deposit. Such a fouled silicone rubber surface typically releases a molded polyurethane article, prepared by the method of Example IXXX- IX, only with difficulty and an inferior decorative definition is imparted to the molded article.

The fouled silicone rubber substrates were then washed for 48 hours at about 25 C. with various acids as shown in Table 4. As the table indicates, most of the acids were used as solutions in various solvents.

As shown in Table 4, all of the washed silicone rubber substrate surfaces easily released the. molded polyurethane articles therefrom after treatment with the acids. Most of the stain on the treated surfaces of the silicone rubber substrate surfaces generally changed color upon treatment. mostly to a yellow or dark brown color. All of the treated surfaces gave the appearance of being clean.

EXAMPLE XLI Successive polyurethane parts were molded on a silicone rubber surface according to the method of Example I, except that toluene was used for the solvent ofthe polyurethane reaction' mixture instead of methylene chloride. The silicone rubber had a Shore A hardness of 45. After about 60-80 parts had been molded in a mold, the mold surface exhibited a cracking or hazing appearance much like large cracks in mud as it dries. The Shore A hardness of the silicone rubber had increased to 50. After about 200 parts the mold surface exhibited blisters and began to chunk and tear apart.

Correspondingly, successive molded parts were molded on the silicone substrate surface except that methylene chloride was used for the solvent of the polyurethane reaction mixture instead of toluene. After 180 parts had been molded in the silicone mold, the mold surface had not even started to crack. The hardness ofthe silicone rubber remained about the same.

For the'purpose of this example the polyurethane reaction mixture was prepared by melting 100 parts of the adipates and degassing at about 80 C. for 1 hour under a reduced pressure. The diisocyanate in the amount of 40 parts was also melted and the adipate and diisocyanate mixed and allowed to react for about 1 hour at 100 to 120 C. The mixture was then degassed for 1 hour at about 100 C. under a reduced pressure and then allowed to cool to 6874 C. The degassed mixture was then dissolved in 140 parts of methylene chloride.

A curative solution was prepared by mixing 20 parts of meta-paraxylene diamine with 80 parts of methyl ethyl ketone.

Just before application to the mold surface, 100 parts of the polyurethane prepolymer were mixed with about l6 parts of the curative solution plus 10 parts of pigment. Upon casting of the mold substrate it was placed in an infrared heated oven at a temperature of about 50 C. for about 3-5 minutes, then removed from the oven and the molded polyurethane article removed from the silicone rubber mold.

The silicone rubber mold was prepared according to the method used in Example I except that it was not further postcured for about three days at about 250 C. and for 8 hours at about 60 C. The liquid room temperature curing silicone rubber used was prepared by mixing components A and B of Silastic E, (obtained from The Dow Corning Company). Component B comprised a platinum catalyst, fillers and oils.

While certain representative embodiments and details have been shown for the purpose of illustrating the invention. it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.

What is claimed is:

l. A method of retarding the fouling of a substrate surface 5 and resulting deposits thereon, where the said fouling and deposits are formed by contacting the substrate surface in the presence of water and carbon dioxide with at least one of the amine compounds consisting of amine compounds having primary amino groups, where the said amine compounds are identified by the test which comprises forming one liter of a solution containing from about to about parts by weight of the amine compound per 100 parts by weight of methyl ethyl ketone, aging the solution for 8 hours at C., warming the solution to C. and passing gaseous carbon dioxide at about 25 C. through the solution at a rate of about one gaseous liter per minute to form a turbidity in the solution within minutes, the method being characterized by treating the said surface and any resulting deposits thereon with at least one organic acid selected from aliphatic dicarboxylic acids having from twoto 10 carbon atoms, tricarboxylic acids having six to 10 carbon atoms, alkanoic acids having from four to eight carbon atoms, unsaturated organic acids having three to eight carbon atoms, chlorosubstituted acetic acid and phenol.

2. The method of claim 1 where the said organic acids are selected from oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, citric, acrylic, crotonic, maleie, fumaric, butanoic, pentanoic, hexanoic, heptanoic, octanoic, chloroacetic, dichloroacetic and trichloroacetic acids.

3. The method according to claim 2 where the said organic acids are selected from aliphatic dicarboxylic acids, unsaturated organic acids and alkanoic acids.

4. The method according to claim 1 where the said organic acid is mixed with an inert solvent.

5. A method according to claim 1 wherein the substituted methyl amine compound is selected from the group consisting ofa compound having the structure and a compound prepared by reacting a substituted methyl amine compound of l) with a compound selected from the group consisting of an aldehyde and a ketone, where R,, R, and R are individually selected from the group consisting of (a) hydrogen radicals, alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals, and (b) substituted alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals where the substituents are selected from at least one of the group consisting of hydrogen, carbon, oxygen, sulfur, fluorine, chlorine, bromine, iodine and phosphorous.

6. A method according to claim 1 where the substituted methyl amine compound is a diamine having amino groups attached to nonbenzenoid carbon atoms.

7. A method according to claim I where the substituted methyl amine compound is selected from the group consisting of ethylene diamine, hexamethylene diamine and dimethyl hexamethylene diamine; isophorone diamine, 1,4-cyclohexane bis methylamine, 4,4'-diamino-dicyclohexyl methane, meta xylene diamine, para-xylene diamine, tetrachloroparaxylene diamine,-cyclobutane-l,2 bis methylamine, menthane diamine, imino bis propylamine, bis (amino propyl) piperazine, diethylene triamine, triethylene tetramine, and tetraethylene pentamine.

8. A method according to claim 7 where the solid substrate surface is selected from at least one of the group consisting of polyethylene, polypropylene, silicone rubber and release agent coated metals, cured millable gum silicone rubber, cured natural rubber, rubberlike polymers, thermoplastic polymeric materials, and thermoset polymeric materials.

9. A method according to claim 8 where the substrate surface is a silicone rubber, and where the organic acid is concentrated.

10. A method according to claim 1 where the fouling and any deposits resulting therefrom are formed by contacting the substrate surface in the presence of water and carbon dioxide with a polyurethane reaction mixture, curing the reaction mixture, and removing the resulting cured polyurethane article from the substrate surface, where the polyurethane reaction mixture contains at least one of the substituted methyl amine compounds.

11. A method according to claim 10 where the substituted methyl amine compound is selected from at least one of the group consisting of ethylene diamine, hexamethylene diamine and dimethyl hexamethylene diamine; isophorone diamine, l,4-cyclohexane bis methyl amine, 4,4'-diamino-dicyclohexyl methane, meta xylene diamine, para-xylene diamine, tetrachloroparaxylene diamine, cyclobutanel ,2 bis methylamine, menthane diamine, imino bis propylamine, bis (amino propyl) piperazine, diethylene triamine, triethylene tetramine, and tetraethylene pentamine.

12. A method according to claim II where the solid substrate surface is selected from at least one of the group consisting of polyethylene, polypropylene. silicone rubber, and release agent coated metals, cured millable gum silicone rubbers, cured natural rubber, rubberlike polymers, therbons. and castor oil, (b) at least one organic polyisocyanate, the overall molar ratio of the isocyanate groups of the polyisocyanate to the reactive hydrogens of the hydrogen-containing polymeric material being between about l.l/l and about l2/l and (c) at least one diamine having amino groups attached to nonbenzoid carbon atoms in a ratio of from about 0.5/1 to about 1.5/1 of amine groups to the isocyanate groups in excess of the reactive hydrogen-containing polymeric material. 

2. The method of claim 1 where the said organic acids are selected from oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, citric, acrylic, crotonic, maleic, fumaric, butanoic, pentanoic, hexanoic, heptanoic, octanoic, chloroacetic, dichloroacetic and trichloroacetic acids.
 3. The method according to claim 2 where the said organic acids are selected from aliphatic dicarboxylic acids, unsaturated organic acids and alkanoic acids.
 4. The method according to claim 1 where the said organic acid is mixed with an inert solvent.
 5. A method according to claim 1 wherein the substituted methyl amine compound is selected from the group consisting of a compound having the structure and a compound prepared by reacting a substituted methyl amine compound of (1) with a compound selected from the group consisting of an aldehyde and a ketone, where R1, R2 and R3 are individually selected from the group consisting of (a) hydrogen radicals, alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals, and (b) substituted alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals where the substituents are selected from at least one of the group consisting of hydrogen, carbon, oxygen, sulfur, fluorine, chlorine, bromine, iodine and phosphorous.
 6. A method according to claim 1 where the substituted methyl amine compound is a diamine having amino groups attached to nonbenzenoid carbon atoms.
 7. A method according to claim 1 where the substituted methyl amine compound is selected from the group consisting of ethylene diamine, hexamethylene diamine and dimethyl hexamethylene diamine; isophorone diamine, 1,4-cyclohexane bis methylamine, 4, 4''-diamino-dicyclohexyl methane, meta xylene diamine, para-xylene diamine, tetrachloroparaxylene diamine, cyclobutane-1,2 bis methylamine, menthane diamine, imino bis propylamine, bis (amino propyl) piperazine, diethylene triamine, triethylene tetramine, and tetraethylene pentamine.
 8. A method according to claim 7 where the solid substrate surface is selected from at least one of the group consisting of polyethylene, polypropylene, silicone rubber and release agent coated metals, cured millable gum silicone rubber, cured natural rubber, rubberlike polymers, thermoplastic polymeric materials, and thermoset polymeric materials.
 9. A method according to claim 8 where the substrate surface is a silicone rubber, and where the organic acid is concentrated.
 10. A method according to claim 1 where the fouling and any deposits resulting therefrom are formed by contacting the substrate surface in the presence of water and carbon dioxide with a polyurethane reaction mixture, curing the reaction mixture, and removing the resulting cured polyurethane article from the substrate surface, where the polyurethane reaction mixture contains at least one of the substituted methyl amine compounds.
 11. A method according to claim 10 where the substituted methyl amine compound is selected from at least one of the group consisting of ethylene diamine, hexamethylene diamine and dimethyl hexamethylene diamine; isophorone diamine, 1,4-cyclohexane bis methyl amine, 4,4''-diamino-dicyclohexyl methane, meta xylene diamine, para-xylene diamine, tetrachloroparaxylene diamine, cyclobutane-1,2 bis methylamine, menthane diamine, imino bis propylamine, bis (amino propyl) piperazine, diethylene triamine, triethylene tetramine, and tetraethylene pentamine.
 12. A method according to claim 11 where the solid substrate surface is selected from at least one of the group consisting of polyethylene, polypropylene, silicone rubber, and release agent coated metals, cured millable gum silicone rubbers, cured natural rubber, rubberlike polymers, thermoplastic polymeric materials, and thermoset polymeric materials.
 13. A method according to claim 12 where the substrate surface is a silicone rubber, where the organic acid is concentrated and where the said polyurethane reaction mixture is prepared from (a) at least one reactive hydrogen-containing polymeric material having a molecular weight between about 700 and about 5,000 selected from the group consisting of polyester polyols, polyester amides, polyether polyols, dihydroxyl-terminated polymer of conjugated diene hydrocarbons, and castor oil, (b) at least one organic polyisocyanate, the overall molar ratio of the isocyanate groups of the polyisocyanate to the reactive hydrogens of the hydrogen-containing polymeric material being between about 1.1/1 and about 12/1, and (c) at least one diamine having amino groups attached to nonbenzenoid carbon atoms in a ratio of from about 0.5/1 to about 1.5/1 of amine groups to the isocyanate groups in excess of the reactive hydrogen-containing polymeric material. 